Oxyalkylated derivatives of certain allyl polymers



April 15, 1952 M. DE GROOTE 2,593,276

OXYALKYLATED DERIVATIVES OF CERTAIN ALLYL. POLYMERS Original Filed July11, 1950 2 SHEET S--SHEET 1 FIG .I

220 1.4900 c X N l: a 1.4950 2 100 1.4940 g 2 u 1.49210 2 O n: z 1401.4920 cc 120 1.4910 u I o 8 100 1.4900 X 3 1.4990 "5 Z so 1.4090 .7 n m40 1.4010

1.4050 20 so 901001201401 so 200 TIME m mmur POLYMERIZATION OFALLYLSUGROSE AT IOOkO.

BLOWN ALLYL I00% C H O SUGROSE 100% Melvin DeGr001e INVENTOR.

AT'ITORNEYS April 15, 1952 M. DE GROOTE 2,593,276

OXYALKYLATED DERIVATIVES OF CERTAIN ALLYL POLYMERS Original Filed July11, 1950 2 SHEETS-SHEET 2 F l G. 3

I00 "/0 PROPYLEN E OXIDE 100% POLYMER Al 0 0M |oo'% ETHYLENE ALLYL ROSEu u or OXIDE A ROSE AND OTHER AL L COMPOUNDS [00% PROPYLENE OXIDE AAAEYA WA AVAV "Z: AVA VAWAMVVA Melvin DeGrooie JNVENTOR.

IO0% POLYMERIZED PENTA- IOOQG ETHY E ALLYLSUGROSE OXIDE W /WV% ATTORNEYS Patented Apr. 15, i952 OXYALKYLATED DERIVATIVES OF CERTAIN ALLYLPOLYMERS Melvin De Groote, St. Louis, Mo., assignor to PetroliteCorporation, Ltd., Wilmington, Del., a corporation of DelawareContinuation of applications Serial Nos. 173,048

and 173,050, July 11, 1950.

This application August 16, 1951, Serial No.242,165

26 Claims. 1

The present invention is concerned with certain new chemical products,compounds or compositions which have useful application in various arts.It includes methods or procedures for manufacturing said new chemicalproducts, compounds, or compositions, as well as the products, compoundsor compositions themselves.

The particular compounds or products herein described in greater detailsubsequently are hydrophile synthetic products; said hydrophilesynthetic products being, oxyalkylation products of (A) an alpha-betaalkylene oxide selected from theclass consisting of ethylene oxide,propylene oxide, butylene oxide, glycide, methylglycide, methyl glycidylether, ethyl glycidyl ether and propyl glycidyl ether; and (B) anorganic solventsoluble, oxyalkylation-susceptible polymerization productof a member of the class consisting of allylsucrose, and allylsucrose incombination with other copolymerizable allyl compounds: in saidcombination the weight percentage of allysucrose being not less than andnot over 90%.

Such products are of particular value for resolving petroleum emulsionsof the water-inoil-type that are commonly referred to as cut oil, roilyoil, emulsified oil, etc., and which comprise fine droplets ofnaturally-occurring waters or brines dispersed ina more or lesspermanent state throughout the oil which constitutes the continuousphase of the emulsion.

This specific application or use of my reagents is described and claimedin my co-pending applications, Serial Nos. 173,047, now Patent No.2,574,544 and 173,049, new Patent No. 2,574,545 filed July 11, 1950.

The compounds or cogeneric mixtures herein described are not only usefulfor breaking oil field emulsions but also are, useful for various otherpurposes, such as a break-inducer in the doctor treatment of sourhydrocarbons, as an emulsifying agent, as a component in the preparationof micellar solutions, as an additive to nonhydrocarbon lubricants, asan intermediate for further reaction by virtue of the terminal hydroxylradical, etc.

The oxyalkylated derivatives may be used for a number of purposes wheresurface-active agents are useful such as the production of agriculturalsprays, emulsions having detersive action, and other comparable uses.Over and above this the products may be'employed to give derivatives ofthe kind described in Part 4 of the present application.

Sub-generically the present invention is concerned with certainhydrophile synthetic prod ucts; said hydrophile synthetic products beingoxyalkylation products of (A) an alpha-beta alkylene oxide selected fromthe class consisting of ethylene oxide, propylene oxide, butylene oxide,

, radicals; with the proviso that the hydrophilev glycide andmethylglycide; and (B) an organic solvent-soluble,oxyalkylation-susceptibl.e, polymerization product of allylsucrose inwhich there is present a plurality of allyl radicals; and with the finalproviso that the hydrophile properties of said oxyalkylated derivativein an equal weight of xylene are sufficient to produce an emulsion whensaid xylene solution is shaken vigorously with one to three volumes ofwater.

The preferred aspect of the invention is concerned with oxyalkylationproducts in which the average molecular weight on a statistical basis,assuming completeness of reaction, is in excess of 10,000. As an examplethe preferred aspect is concerned with certain hydrophile syntheticproducts; said hydrophile synthetic products being oxyalkylationproducts of (A) an alpha-beta alkylene oxide selected from the classconsisting of ethylene oxide, propylene oxide, butylene oxide, glycide,methylglycide, methyl glycidyl ether, ethyl glycidyl ether and propylglycidyl ether; and (B) an organic solvent-soluble,oxyalkylation-suseptible polymerization product of a member of the classconsisting of allylsucrose, and allylsucrose in combination with othercopolymerizable allyl compounds; in said combination the weightpercentage of allylsucrose being not less than 10% and not over and withthe proviso that the molecular weight of the oxyalkylation products onan average statistical basis, assuming completeness of reaction, it isin excess of 10,000.

Likewise, more specifically the preferred aspect is concerned withcertain hydrophile synthetic products; said hydrophile syntheticproducts being oxyalkylation products of (A) an alpha-beta alkyleneoxide selected from the class consisting of ethylene oxide, propyleneoxide, butylene oxide, glycide and methylglycide; and (B) an organicsolvent-soluble, oxyalkylation-susceptible polymerization product ofallylsucrose in which there is present a plurality of hydroxylproperties of said oxyalkylated derivative in an equal weight of xyleneare sufficient to produce an emulsion when said xylene solution isshaken vigorously with one to three volumes of water;

and with the final proviso that the molecular weight of theoxyalkylation products on an average statistical basis, assumingcompleteness of reaction, is in excess of 10,000.

A particularly important group of compounds are xylene solubleoxyalkylation derivatives obtained by reacting (a) polymerizedpentallylsucrose with (b) an alkylene oxide selected from the classconsisting of propylene oxide alone and propylene oxide in combinationwith ethylene oxide, with the proviso that polymerized allylsucrose doesnot contribute more than 15% of the final weight of the oxyalkylationderivative based on the assumption of completeness of reaction and on anaverage statistical basis; and with the final proviso that the ultimatecomposition comes within approximately the trapezoidal area of points A,B, C, D, in the accompanying Figure 4 of the hereto attached drawing.

For convenience, what is said hereinafter will be divided into fourparts:

Part 1 is concerned with the preparation of allylsucrose and thedescription of other allyl compounds which are co-polymerizable withallylsucrose;

Part 2 is concerned with the polymerization or blowing of allylsucrose,or co-polymerizable mix-' tures of allylsucrose or other allylderivatives;

Part 3 is concerned with the oxyalkylation of the polymerized or blownallylsucrose or allylsucrose mixtures, and

Part 4 is concerned with certain derivatives obtained by the use of theherein described oxyalkylated polymerized allylsucrose or allylsucrosemixtures.

PART 1 The preparation of allylsucrose has been described in'theliterature. See Industrial and Engineering Chemistry, volume 4'1, p.1697, August 1949, and Sugar, volume 42, No. 9, p. 28 (1947). Ithas'been described also in a pamphlet distributed by the Sugar ResearchFoundation, Inc., 52 Wall Street, New York city, N. Y., entitled'Preparation and Properties of Allyl Sucrose.

It is'expe'cted that this product will be available Table -I.Preparation of allylsucrose with allyl chloride Analysis of Products,gfi Allyl Groups g Auto- Y Chlorrde/ Cent of clave [Ole From HvdroxylTheo Sucrose .Direct Hydroxyl Groups retical Monel. s 4.17 5. 7 2. 3Monel. l 4. 8 (S. l 1.9 81 Monel. I2 '5. 2 6.3 l. 7 90 Glass 12 15.".86. l l. 9 '84 MoneL. 16 5. 6. 6 1.4 90

.Aswith allyl bromide, apparently the optimum amountof allyl "chlorideis 12 moles per moleof sucrose. Allylsucrose was preparedas follows:

l. Sucrose (l000grams, 2.9.moles) was added with mechanical stirring toa mixture of 1402 gramsi(-35.0 moles) of sodium hydroxide and 700mlwofwateratroom temperature in a 2-gallon, glass-lined autoclaveequipped with a-stirrer and ajacket connectedto steam and cold waterinlets. Allyl chloride (2680 grams, 35.0 moles) was'lthenadded andtheautoclave was sealed and-heated to'.85 .C. =(jacket temperature). At

the beginning of the reaction and up to about 45 to 50 a valve at thetop of the autoclave remained open until the vapors of allyl chloridestarted to condense at the tip of the valve. Heating during the initialstage of the reaction was carefully controlled, since the reaction isexothermic and a rise in temperature above 83 C. darkens the productconsiderably. Within 1.5

hours the thermometer well temperature was 82 C., and the internalpressure increased rapidly to 20 per square inch. At this point coldwater was circulated through the jacket to moderate the reaction. Afterthis exothermic stage was passed, the well temperature was easilycontrolled at to 82 C., for 5.5 hours longer. At the end of 8 hours thewell temperature was 81 C., and the pressure was down to about 4 pounds.Heating was discontinued at this point, and the autoclave was allowed tocool. The autoclave was then opened and filled with water, withstirring, to dissolve the sodium chloride. The organic layer wasseparated, steam-distilled, washed with water and treated as describedfor the allyl bromide preparation. The yield of light brown oil was 1400grams (835% of theoretical) with refractive index (12 and 1.4920. Itcontained 5.8 allyl groups and 1.9 hydroxyl groups.

2. Sucrose (500 grams, 1.5 moles) was added with motor stirring to amixture of -701 grams (17.5 moles) of sodium hydroxide and 350 ml. ofwater at room temperature in a l-gallon, jacketed, Monel metalautoclave. Allyl chloride (1340 grams, 17.5 moles) was added, and theautoclave was sealed and heated to 85 C. (jacket temperature) for -8hours. 'Because of the better heat transfer of this autoclave, it wasnot necessary at any time to cool the jacket to moderate the reaction.Within l.75hours the internal pressure reached 25 pounds per squareinch, and the well temperature was 82 C. At the end of 8 hours thepressure was down to about 4 pounds and the well temperature was 78 C.The autoclave was then cooled and filled with water to dissolve thesodium chloride, and the product was treated as described above. Theyield of light brown oil was 783 grams of theoretical) n =l.4960. Thenumber of allyl groups was 5.2; the numberof hydroxyl groups, 1.7.

The allyl content was determined as de scribed previously; the hydroxylcontent was determined by the method described by Qgg, Porter, andWil1its.**

As has been pointed out previously allyl. sucrose can be polymerizedalone or in conjunction with other well-known polymerizable allylcompounds. Such other-allyl compounds which can be employed in admixturewith -allylsucrose may or may not contain hydroxyl-radicals, or for thatmatter,=-some other radical such as acarboxyl radical or a radical withhydrogen bound to nitrogen which .is also susceptible to oxyalkylation.Some of these compounds-will be described subsequently but in :the mainthe procedure of preparing such compounds is well known. In connectionwith such allyl derivatives reference is made to apamphletentitled AllylAlcohol," issuedby Shell fChemicalgCorporation, 500 Fifth Avenue,iNewYork 18, N. Y.,

*Nichols, -P. L, Jr., and Yanovsky, Elias, J. Am.

Chem. Soc, 67, 4c (1945).

** o 1)., Porter, W L., and Willits, c.- 0., Ind.

Eng-Chem Anal 'Ed.,-1 7, 394 (1945)."

See also Journal American .Chemical v a Company, 500 Fifth Avenue, NewYork 18, N. Y. See also Data Sheet DS-48z22, Allyl Glycidyl Ether, ShellChemical Company, 500 Fifth Avenue, New York 18, N. Y. Various methodsemployed for producing suitable allyl compounds include the following:

(1) The esterification of allyl alcohol with a monocarboxy acid such asa higher fatty acid, including oleic acid, ricinoleic acid, etc.

(2) The esterification of allyl alcohol with the acid ester of apolyhydroxy acid such as glycerol monophthalate, diglycerolmonosuccinate, etc.

(3) The reaction involving an alkoxide and allyl chloride (seemanufacture of allylsucrose above).

(4) The reaction involving the alkoxide of allyl alcohol and a reactivehalogen. (See the preparation of diallyl glycerol in the above notedJournal of American Chemical Society reference.)

(5) The use invovling 1-allyloxy-3-chloro-2- propanol.

(6) Reactions involving compounds such as 1,3-dich1oropropene.

(7) Allyl alcohol can be treated with alkylene oxides, such as ethyleneoxide, propylene oxide, butylene oxide, glycide, etc. The residualhydroxyl group can be used as an intermediate for further reaction.Allyl alcohol can be treated also with epichlorohydrin, or similarchloroepoxy compounds, so as to give derivatives in which furtherreaction may involve not only the hydroxyl radical but also the chlorineatom, or both.

(8) Numerous other reactions are included in the literature andparticularly the patent literature of allyl resins. In many instancesthe most satisfactory procedure is to employ allyl glycidyl ether(1-allyloxy-2,3-epoxypropane) Subsequently there is described in part 3procedures involving oxyalkylation, and particularly oxyalkylationinvolving the use of glycide. The use of allyl glycidyl ether iscomparable to the use of glycide. In other words, in the properly chosenreactions a double bond is not involved but only the high reactivity ofthe epoxide group. Like glycide, or for that matter any other reactivealkylene oxide, allyl glycidyl ether generally does not require the useof a catalyst, particularly an alkaline catalyst, when used inconnection with basic nitrogen compounds for instance a reactioninvolving triethanolamine.

In the treatment of suitable reactants with allyl glycidyl ether thesame precaution should be taken, or even greater precaution, than in theuse of glycide. If in doubt an initial exploratory synthesis should beundertaken with due precaution and particularly with a means ofcontrolling the heat involved so the speed of reaction can becontrolled. Suitable reactants for reaction with allyl glycidyl etherare so numerous that they may be simply indicated as substantially allthose which are reactive towards glycide. Generally speaking, thisincludes almost all compounds having a reactive hydrogen (hydrogenattached to nitrogen, oxygen or sulfur) and in some instances compoundsnot apparently showing a reactive hydrogen atom. Particularly suitableare materials such as glycerol, diglycerol, higher polyglycerols,sucrose, sorbitol, sorbitan, mannitol, mannitan, etc. Similarly one mayemploy the same compounds which have been treated with an alkylene oxideother than allyl glycidyl ether, such as ethylene oxide, propyleneoxide, glycide, etc. Other compounds particularly suitable includepentaerythritols, polypentaerythritols, glucose, sugar derivatives suchas glycol glucosides of the kind described in U. S. Patents 2,407,001,2,407,002, and 2,407,003 dated September 3, 1946, to Grifiin,tetramethylol cyclohexanol, and ally starch.

Other materials which may be treated with alkylene oxides so as tochange-their nature and particularly so as to render them morehydrophile and usually water-soluble, are described in numerous patents,such as British Patents Nos. 341,516, 364,323, 368,530, 380,851, and411,474. (See also U. S. Patent No. 1,596,785 dated August 17, 1926, toWeyland.) The materials so in cluded cover such diverse products asglue, gelatin, starch, dextrine, alkyl glucosides, albuminous materials,cellulose derivatives soluble in water and soluble in alkali, and alsothose soluble in nonaqueous solvents, casein, horn, wool, hair, etc.This applies also to synthetic products such as resins, particularlyphenolaldehyde resins or dimers derived from phenols Y and aldehydes,linear polyamides such as those derived from diamides and dicarboxyacids. This applies also to glycoside ether from. polysaccharide ethers,etc., as outlined in U. S. Patent No. 2,258,168 dated October 7, 1941,to White.

Other compounds susceptible to treatment with allyl glycidyl etherinclude phenols, substituted phenols, cyclic alcohols such as terpineol,tetrahydrofurfuryl alcohol, hydrogenated phenols, etc. Acids (eithermonocarboxy or polycarboxy) can be reacted with these reagents.Similarly, amines such as tertiary amines containing at least onealkanol radical, or primary or secondary amines which contain an aminohydrogen atom and may or may not contain an alkanol radical, can beused. This applies to polyamines as well as monoamines, mercaptans, suchas decyl mercaptan, dodecyl mercaptan, etc.

Allyl glycidyl ether can be reacted with numerous other cellulosederivatives such as those described in U. S. Patents Nos. 2,033,126,2,135,128, 2,157,530, 2,055,893 and 2,136,296.

Obviously, the various materials previously described can be convertedinto derivatives having an amino radical or the number of amino radicalscan be reversed by reaction with ethylene imine or propylene imine.

Needless to say, such allyl derivatives of the kind enumerated above andintended for use as in preparing a copolymerizable mixture withallylsucrose may be polymerized alone in absence of allylsucrose.Similarly, mixtures of the allyl compounds other than allylsucrose, maybe copolymerized to give suitable polymers. In any event, such polymersobtained, in the absence of allylsucrose, from one or more of the allylcompounds or similar allyl compounds can be oxyalkylated in the mannerdescribed subsequently in Part 3 so as to yield valuable oxyalkylationderivatives. The products so obtained are useful not only for thepurpose of resolving oil field emulsions in the same manner as describedin Part 4 but also for other uses such as making emulsions or acting asan emulsion promoter or additive in conjunction with other emulsifyingagents. agents and also as intermediates for further reaction throughthe terminal hydroxyl radical. In all such instances polymerization canbe promoted by peroxide catalysts as well as by blowing. Allylsucrose,as is obvious in light of what They may be used as deilocculatinghasbeen said previously, is used in two definite senses; one to mean aspecific allylsucrose, for instance, penta-allylsucrose specifically;and generically to mean any allylsucrose, or for that matter a cogenericmixture of one or more allylsucroses. However, this does not lead toconfusion because the sense of the text in each instance is obvious.

As examples of suitable mixtures the ,following are included for purposeof illustration:

EXAMPLE 1a 750 grams of allylsucrose (principally pentaallylsucrose)were mixed with an equal part of diallyl glycerol. This mechanicalmixture was used subsequently in-the same manner as allylsucrose.

'The above applies to subsequent examples in which no more data will begiven other than mixture ratios as they are mechanical mixtures andnothing more.

EXAMPLE 2a Sorbitol was reacted in presence or of sodium methylate with4 moles of allyl glycidyl ether. 750 grams of this end product weremixed with 750 grams of allylsucrose (principally penta allylsucrose)EXAMPLE 3a Sorbitol was reacted with 6 moles of ethylene oxide and theresultant product reacted with 4 moles of allyl glycidyl ether.Oxyethylated sorbitol is .available commercially or canbe prepared bywell known methods. The treatment with allyiglycidyl ether was in thepresence of sodium methylate by conventional procedure. 500 grams ofthis material were mixed with 1,000 grams of allyl-sucrose (principallypenta-allylsucrose).

EX MPLE 4 Tetramethylol cyclohexanol was reacted with 3 moles of allyl.glycidyl ether. The reaction was conducted in the same manner aspreviously described. 1,000 grams of this material were mixed with 50.0grams of allylsucrose (principally penta-allylsucrose) EXA PLE 5aPentaerythritol was reacted with 4 moles of ethylene oxide and 4 molesof allyl glycidyl ether. 750 grams of this material were mixed with 750grams of allylsucrose (principally penta-allyl sucrose)' 7 EXAMPLE 6aTriglycerol obtained by reacting 2 moles of glycide to one mole ofglycerol was reacted with 3 moles of allyl glycidyl ether. 650 grams ofthis product were mixed with 850 grams of allylsucrose (principallypenta-allylsucrose EXAMPLE 7a 150 grams of allyl oleate were mixed with1350 grams of allylsucrose (principally penta-allyl- M053 EXAMPLE 8aGlycerol alpha-allyl ether is mixed with allylsucrose (principallypenta-allylsucrose) in the ratio of 1200g rams of allylsucrose and 300grams of glycerol alpha-allyl ether.

EXA LE. Triethanolamine is treated with allyl glycidyl ether in theratio of 3 'moles of the ether forone mole of the triethanolamine. 300grams of this material are mixed with 1200 grams of allylsucrose(principally penta-allylsucrose) EXAMPL 10a 1100 parts of allylsucrose(principally penta 8 allylsucrose) were mixed with 200 parts of diallylglycerol and 200 parts of glycerol alpha-allyl ether.

EXAMPLE 11a One mole of allyl alcohol was reacted with one mole of allylglycidyl ether so as to produce a compound having two allyl groups andone hydroxyl radical. grams of this material were mixed with 1150 gramsof allylsucrose (prim cipally penta-allylsucrose).

EXAMPLE 12a 150 grams of allyl starch (General Mills, Inc., Minneapolis,Minnesota) were mixed with 1150 grams of allylsucrose (principallypenta-allylsucrose) See Industrial and Engineering Chemistry, volume 35,page 2 01 (1945).

EXAMPLE 13a Allyl oleate was heated to 125 C., and blown with air for100 hours. At the end of this time the product had turned from a paleYQHOW to an almost black viscous liquid and indicationswere that furtherblowing would cause a stringy polymer. 200 grams of this material weremixed with 1000 grams of allylsucrose (principally penta-allylsucrose).

EXAMPLE 14a Allyl ricinoleate was blown in the same manner as indicatedin Example 13a, preceding, except that blowing was stopped at the end of8 hours. This particular product did not discolor and also approachedjust short of the stringy stage in 20% less time than in the case of theoleate. 250 grams of this product were mixed with 1250 grams ofallylsucrose (principally penta-allylsucrose).

EXAMPLE 15a An allyl naphthenate was prepared from a light colorednaphthenic acid obtained from California crude and sold by the OroniteChemical Company, San Francisco, California, under the designation L.The specifications on this particular naphthenic acid are as follows:

This particular allyl compound was blown for .87 hours until just shortof the stringy stage. 'It discolored only slightly. 250 grams of thisblown product were mixed with 1250 grams of allyl sucrose (principallypenta-allylsucrose) EXAMPLE 1631 250 grams of glycerol alpha-allyl ethermonooleate were mixed with 1250 grams of allylsucrose (principallypenta-allylsucrose).

EXAMP E 250 grams of glycerol alpha-allyl ether mono-- ricinoleatewere'mixed with 1250 grams of sucrose (principally penta-allylsuc'rose).

EXAMPLE 1 8a 250v grams of glycerol alpha-allyl ether monornaphthenatewere mixed with 1250 grams of allyl,- sucros'e (principallypenta-allylsucrose). The naphthenic acid used to form the fractionalester was the particularone described under the heading of Example 1 5a,preceding.

Diallyl catechol was blown for 45 hours. At

- the end of this time the product was a semirubbery mass. Thetemperature of blowing was 110 C. The process was repeated and theoxidiz ing stopped 8 hours short of the previous stage, i. e., at theend of 37% hours.

with 1250 grams of allylsucrose (principally penta-allylsucrose) As tothe preparation of diallyl catechol, and

diallyl resorcin, see U. S. Patent No. 2,459,835,

dated January 25, 1949, to Monroe.

Needless to say, mixtures containing an allylsucrose need not be binarymixtures but can have three or more components, as, for example, amixture consisting of one-third each of allylsucrose, diallyl glyceroland the sorbitol derivative described in Example 2a, preceding. A morecomplex mixture would consist of one-fourth part each of allylsucrose,diallyl'glycerol, the sorbitol derivative as described under the headingof Example 2a, and the tetramethylol cyclohexanol mixture describedunder the heading of Example 4a.

PART 2 In regard to polymerization of allylsucrose reference is madeagain to the aforementioned Zief and Yanovsky article in Industrial andEngineering Chemistry.

The following table, data, etc., are in substantially verbatim form asthey appear therein:

POLYMERIZATION A previous article pointed out that for someapplications-for example, coating materials-it is advisable to oxidizethe product partially to increase viscosity. Since, during this partialpolymerization, the refractive index increase parallels the increase inviscosity, by observing the change in refractive index and in- 250 gramsof this partially polymerized diallyl catechol were mixed tentviscosity, refractive index, and gelation time, reproducible resultswere obtained wheneverthe partial polymerization was interrupted at thesame refractive index.

Allylsucrose prepared in a glass-lined autoclave with allyl chloride hasa lower allyl content than the products prepared with allyl bromide and,hence, gives diiferent values for viscosity, refractive index, andgelation time. viscosity-refractive index curves will, therefore, besomewhat different from those in Figure 1 but will serve the samepurpose. The curves for allylsucrose made in a Monel metal autoclavewill also be different for, in addition to having a different degree ofallylation, the product will be partially polymerized.

The point at which the preliminary polymerization is stopped isdetermined by two' factors."

The closer the refractive index is to the gelation point, the quickerwill the film of allylsucrose be come tack-free on exposure to air. Thusa 50% solution of allylsucrose in toluene or turpentine (having arefractive index of 1.4940) with 0.1% of cobalt (as naphthenate oroctoate) dried tackfree in to 90 minutes at room temperature.

On the other hand, allylsucrose, particularly when partiallypolymerized, has a tendency to polymerize and eventually gel, even atroom temperature. It is important, therefore, to know how long thepolymerized substance will be kept before use.

The effect of storage on monomeric and partially polymerized allylsucrose was investigated. Allylsucrose (6.7 allyl groups) waspolymerized at 100 C. At several points (Figure 1) 25-cc samples werewithdrawn, put into glass vials closed with plastic screw caps, andstored. on a laboratory shelf at room temperature (about 25 C.). Fromtime to time the index of refraction of each sample was examined. TableII gives the results.

Table II shows clearly that, whereas the allylsucrose as prepared(sample 1)- scarcely changed during a year of storage, the partiallypolymerized samples of refractive index 1.4920 or higher gelled atvarious intervals during this period; the sample of refractive index1.4911 closely approached the gelation point after 12-month storage.Although sample 7 gelled in about 4 months, 50% solutions of the samesamples in toluene and turpentine showed no sign of gelation after ayear of storage.

Table II.-Change in refractive index of allylsucrose during storage V[Refractive index, ma a] 50% soln. of No. 7 in:

Turpentine Toluene Q.

*Nichols, 1. L., Jr.,'and Yanovsky, Elias, Sugar, 42, No. 9, 28 (1047).

terrupting the oxidation at a standard value, uniform results will beobtained. Figure 1 shows the viscosity and refractive index curves for alaboratory batch of allylsucrose made with allyl bromide. Sincelaboratory preparations are (Hereto attached Figure 1 corresponds toFigure l in the text of the original article.)

The semi-commercial samples of allylsucrose available appear to containa small amount of volatile aromatic solvent. The actual blowing fairlywell standardized with regard to allyl con- 75 operation appears to bechecked until this bit of The aromatic solvent has been blown out. Such'al' lylsucrose can, of course, be blown with or without agitation.Agitation in essence speeds up the polymerization reaction for obviousreasons. It is in essence more Vigorous blowing conveniently controlled.In the aforementioned Zief and Yanovsky article referred to in detailabove it is, of course, obvious that these investigators were interestedperhaps primarily in obtaining a material suitable as a coating. Thismeant that the blowing operation might well be conducted with a view ofpreventing darkening and also with a View of obtaining material whichwas still uniformly soluble in a solvent, such as toluene or xylene.merized allylsucrose is nothing more than an intermediate for furtherreaction. Color or solubility of the kind which might be desirable in acoating is not critical for the instant purpose.

In the instant invention blown or poly- In the above experiment thechange in refractive index after about 45 minutes of blowing probablymeant that all the solvent present had been eliminated. Also, note that,when the oxidation stage, which required about 9 hours in all,

what is said in regard to such characterization Below are three typicalexamples in which various degrees of polymerization have been obtainedby blowing. Allylsucrose or allylsucroses can be polymerized byperoxides such asbenzoyl peroxide, in a conventional manner but theprocedure is less satisfactory than air-blowing. The final resultantproducts are probably substantially identical provided, of course, thatthe peroxide polymerization has not been conducted so as to result in aninsoluble compound or mixture. It is hardly necessary to add to what hasappeared in the literature in regard to the art of polymerization byblowing of allylsucrose but the following examples are included forillustration and for the reason that cognizance has been taken of thefact that allylsucrose (approximately 5,.allyl groups on theaverage persucrose molecule) is somewhat dispersible in water, and also somewhatdispersible in the initial stage of polymerization. However, in thelatter stage of oxidation or polymerization this is not true as isillustrated by the subsequent examples. These various allyl compoundsvcan be polymerized in the same manner employed to polymerize allylesters. See U. S. Patent No. 2,374,081, dated April 17, 1945, to Dean.

EXAMPLE 1b Index of Temperature, Time, Water 0. Minutes 353 Solubility 00 Dispersible.

1. 4883 D0. 1. 4887 D0. 75 1. 4880 Do.

180 l. 4895 Do.

330 l. 4900 Do.

360 l. 4907 Do.

420 1.4922 Less disp'ersible.

440 l. 4937 Insoluble.

480 l. 4950 Do.

in the discussion of the next example.

EXAMPLE 2?) The same procedure was employed as in Example lb except thata stirring device was included along with'the distributing vent. In thisinstance the temperature was held at 130 C. for

'three hours, at the end of which time the product still showeddispersibility. It was then held at for two more hours. At the end ofthis time the product was not water-soluble'andwas very stringy or evensemi-rubbery. When diluted with'an equal weight of xylene the dilutesolu tion was still very viscous and somewhat rubbery. The refractiveindex was 1.4985. Note that this is a higher figure than is shown in thetable referred to in the article by Zief and Yanovsky. For purpose ofconvenience in referring to blown allylsucrose I have used terminologysomewhat comparable to that applied in regard to other blown products,such as blown castor oils. I have considered a product which is blown tojust short of the rubbery stage and is exemplified by Example 11),preceding, as mildly oxidized, mildly blown or mildly polymerized. Ihave used the expression drastic polymerization to indicate a productwhich is not only stringy or rubbery as such but also is highly viscousand shows stringiness or rubberiness in a 50% xylene solution or as asolution in other suitable solvents. Such stage istypified by thepresent example, i. e., Example 21).

I have used the expression semi-drastically blown, or semi-drasticallypolymerized, to indicate a productwhich shows incipient stringiness assuch but where such stringiness disappears on dilution. Such product isillustrated by the next example.

EXAMPLE 3?) The same procedure was employed in every respect as inExample 21) except. that the second stage of oxidation at 100 C. waspermitted to take place for 1 hours only instead of 2 hours, and therefractive index at the end of this time was 1.4980 The product showed adefinite tendency to string or rubberize'but this property practicallydisappeared when a 50 solution in xylene was prepared.

Actually blowing or polymerizing can be conducted with ozone or ozonizedair as well as air which may or may not have its moisture contenteliminated. In this particular type of reaction I have found noadvantage in going to any added cost in regard to the oxygenatingprocedure which initiates polymerization. In the polymerization ofcompounds in which basic amino radicals are present I prefer to use airwhich has been have not found this particularly desirable. Since it isusually intended to stop the polymerization at some particular point byuse of a mild blowing or semi-drastic blowing, or a drastic blowing, itis of greater convenience to approabh the end point slowly rather thanrapidly, and also to have polymerization cease when the air streamstops. Referring again to the development of allylsucrose, as has beenpointed out, one of the objectives appears to be concerned with asuitable coating material. Everything else being equal presumably thefewer hydroxyl radicals available in the coating material the better. Onthe other hand as an intermediate reactant this need not apply. Sucroseas an initial raw material has 8 hydroxyl radicals. Diallyl-sucrose, ofcourse, would have an excess of hydroxy1 radicals over allyl radicalsand would not possibly be particularly suitable for a coating material.This does not apply to its use as an intermediate as herein described.The same would be true of triallylsucrose or tetra-allylsucrose. Theproduct now available in at least pilot plant quantities and perhapsshortly in commercial quantities appears to be largely thepenta-allylsucrose with some tetra-allylsucrose, and possibly somehexaallylsucrose present, with perhaps minor amounts or almostinsignificant amounts of other allylsucroses. Tetra-allylsucrose, inwhich the allyl radicals and the hydroxyl radicals are equal, is aparticularly suitable reactant. In penta-allylsucrose andhexa-allylsucrose there are more allyl radicals than hydroxyl radicals.The eifect of this variation in the molecule is significant,particularly insofar that it affects the molecular weight of theultimate. oxyalkylated product described subsequently in at least twoways: (a) The more hydroxyl radicals the more long ether chains whichcan be added per molecule. (1)) On the otherhand the more allyl radicalsprobably the larger the polymerized molecule although this may not betrue. It may be better to assume the more allyl radicals the morereadily the product can be blown or polymerized. Excessivepolymerization eliminates solvent solubility. The product resulting frompolymerization must meet this solubility test, and must also besusceptible to oxyalkylation in absenceof a solvent and particularlyoxyalkylation in presence of a solvent.

There is a fairly narrow range where the product if given super-drastictreatment is only partially soluble at the most in xylene or the likebut is still soluble, at least sufficient for the purpose, in asemi-polar solvent such as dioxane, ethylene glycol diethyl ether,diethylene glycol diethyl ether and tetraethylene glycol dimethyl ether.

Other solvents include hydrogenated aromatic materials such as tetralinand decalin, and ethers containing an aromatic radlical such asptertamylphenyl methyl ether, p-tert-amylphenyl n-butyl ether, n-butylphenyl ether, or more highly oxygenated solvents obtained by treatingbenzyl alcohol or phenol or alkylated phenol with l, 2 or 3 moles of analkylene oxide, such as ethylene oxide or propylene oxide, followed bymethylation so as to convert the terminal oxygenlinked hydrogen atominto a methyl radical.

'Stringiness or rubberiness as described above is probably an indicationof incipient cross-linking or gelation. In any event the allylsucrosesand particularly those having a plurality of allyl groups asdiiferentiated from monallylsucrose, can be divided into three classes:(1) Those in which there are more hydroxyl radicals than allyl radicals,with (2) the number of hydroxy radicals and allyl radicals approximatelyequal, and (3) where the number of allyl radicals are greater thanhydroxyl radicals. As previously stated, the commercial product orsemi-pilot plant prod not now available is on a statistical basisapproximately penta-allylsucrose and in actual composition representsprimarily penta-allylsucrose with some hexa, some tetra, and perhapsother allyl compounds present.

Incipient polymerization means dimerization and trimerization. It isprobable that in the procedure above described that higher polymers suchas tetramers, pentamers, etc., are formed to a greater or lesser degree.However, at some subsequent stage as soon as more than incipientcross-linking takes place the polymers are no longer soluble in xyleneor in some of the semipolar solvents described, or in a mixture ofthetwo. It is to be noted that the solvents of the semi-polar type arecharacterized by the fact that they may be present in the subsequentoxyalkylation step and are not susceptible to oxyalkylation. It is to benoted also that in the subsequent description of the oxyalkylation step(Part 3) it becomes obvious that with a tetramer or pentamer andprobably even in the case of a trimer, one may readily obtainderivatives in which the molecular weights are in the neighborhood of100,000 or thereabouts.

PART 3 Numerous derivatives of the kind described in Part 2, preceding,have been prepared on a scale varying from a few hundred grams on alaboratory scale to larger amounts. This applies also to the preparationof oxyalkylated compounds of the kind or type comparable to those withwhich this third part of the text is concerned. In pre-' paring a largenumber of examples I have found it particularly advantageous to uselaboratory equipment which permits continuous oxypropylation andoxyethylation. More specific reference will be made to treatment withglycide, subsequently in the text. The oxypro'pylation step is, ofcourse, the same as the oxyethylation step insofar that two low boilingliquids are handled in each instance. What immediately follows refers tooxyethylation and it is understood that oxypropylation can be handledconveniently in exactly the same manner.

The oxyethylation procedure employed in the preparation of derivativesof the preceding intermediates has been uniformly the same, particularly in light of the fact that a continuous operating procedure wasemployed. In this particular procedure the autoclave was a conventionalautoclave, made of stainless steel and having a capacity ofapproximately one gallon, and a working pressure of 1,000 pounds gaugepressure. The autoclave was equipped with the conventional devices andopenings, such as the variable stirrer operating at speeds from 50 R. P.M. to.500 R. P. M., thermometer well and thermocouple for mechanicalthermometer; emptying outlet; pressure gauge, manual vent line; chargehole for initial reactants; at least one connection for conducting theincoming alkylene oxide, such as ethylene oxide, to the bottom of theautoclave; along with suitable devices for both cooling and heating theautoclave, such as a cooling jacket and, preferably, coils in additionthereto, with the jacket so arranged that it is suitable for heatingwith steam or cooling with water, and further equipped with electricalheating devices. Such autoclaves are, of course, in essence small scalereplicas of the usual conventional autoclave used in oxyalkylationprocedure.

Continuous operation, or substantially continuous operation, is achievedby the use of a separate container to hold the alkylene oxide beingemployed, particularly ethylene oxide. The container consistsessentially of a laboratory bomb having a capacity of about one-halfgallon, or somewhat in excess thereof. This bomb was equipped, also,with an inlet for charging, and an outlet tube going to the bottom ofthe container so as to permit discharging of alkylene oxide in theliquid phase to the autoclave. Other conventional equipment consists, ofcourse, of the rupture disc, pressure gauge, sight feed glass,thermometer connection for nitrogen for pressuring bomb, etc. The bombwas placed on a scale during use and the connections between the bomband the autoclave were flexible stainless hose or tubing so thatcontinuous weighings could be made without breaking or making anyconnections. This also applied to the nitrogen line, which was used topressure the bomb reservoir. Tothe extent that it was required, anyother usual conventional procedure or addition which provided greatersafety was used, of course, such as safety glass, protective screens,etc.

With this particular arrangement practically all oxyethylations becameuniform in that the reaction temperature could be held within a fewdegrees of any selected point in this particular range. In the earlystages where the concentration of catalyst is high the temperature wasgenerally set for around C. or thereabouts. Subsequently temperatures upto C. or higher may be required. It will be noted by examination ofsubsequent examples that this temperature range was satisfactory. In anycase, where the reaction goes more slowly a higher temperature may beused, for instance, 165 C. to C'., and if need be C. to C. Incidentally,oxypropylation takes place more slowly than oxyethylation as a rule andfor this reason We have used a temperature of approximately 160 C'. to165 C., as being particularly desirable for initial oxypropylation, andhave stayed within the range of 165 C. to 185 0., almost invariablyduring oxypropylation. The ethylene oxide was forced in by means ofnitrogen pressure as rapidly as it was absorbed as indicated by thepressure gauge on the autoclave. In case the reaction slowed up thetemperature was raised so as to speed up the reaction somewhat by use ofextreme heat. If need be, cooling water was employed to control thetemperature.

As previously pointed out in the case of oxypropylation asdifferentiated from oxyethylation, there was a tendency for the reactionto slow up as; the temperature dropped much below the selected point ofreaction, for instance, 170 C. In

this instance the technique employed was the same asbefore, that is,either cooling water was cut down or steam was employed, or the additionof propylene oxide speeded up; or electric heat used in addition to thesteam in order that the reaction proceeded at, or near, the selectedtemperatures to be maintained.

inversely, if the reaction proceeded too fast regardless of theparticularalkylene oxide, the amount of reactant being added, such asethylene oxide, was cut down or electrical heat was cut off, or steamwas reduced, or if need be, cooling water was run through both thejacket and the cooling coil. All these operations, of course, aredependent-on the required'number of conventional gauges, check valves,etc., and the entire equipment, as has been pointed out, is conventional and, as far as we are aware, can be furnished by at least twofirms who specialize in the manufacture of this kind of equipment.

Attention is directed to the fact that the use of glycide requiresextreme caution. This is particularly true on any scale other than smalllaboratory or semi-pilot plant operations. Purely from the standpoint ofsafety in the handling of glycide, attention is directed to thefollowing: (a) If prepared from glycerol monochlorohydrin, this productshould be comparatively pure; (1)) the glycide itself should be as pureas possible as the effect of impurities is difficult to evaluate; (c)the glycide should be introduced carefully and precaution should betaken that it reacts as promptly as introduced, i. e., that no excess ofglycide is allowed to accumulate; (d) all necessary precaution should betaken that glycide cannot polymerize per se; (e) due to the high boilingpoint of glycide one can readily employ a typical separatable glassresin pot as described in U, S. Patent No. 2,499,370, dated March 7,1950, and offered for sale by numerous laboratory supply houses. If sucharrangement is used to prepare laboratory scale duplications, then careshould be taken that the heating mantle can be a removed rapidly so asto allow forcooling'; or better still, through an added opening at thetop the glass resin pot or comparable vessel should be equipped with astainless steel cooling coil so that the pot can be cooled more rapidlythan mere removal of mantle. If a stainless steel coil is introduced itmeans that conventional stirrer of the paddle type is changed into thecentrifugal type which causes the fluid or reactants to mix due toswirling action in the center of the pot. Still better, is the use of alaboratory autoclave of the kind previously described in this part; butin any event, when the initial amount of glycide is added to a suitablereactant, such as a polymerized allylsucrose or a polymer derived froman allylsucrose mixture, the speed of reaction should be controlled bythe usual factors, such as (a) the addition of glycide; (b) theelimination' of external heat, and (0) use of cooling coil so there isno undue rise in temperature. All the foregoing is merely conventionalbut is included due to the hazard in handling glycide.

As has been pointed out previously oxyalkylation involving the use ofallyl glycidyl ether is conducted in a manner similar to glycide,although in'the main this latter reactant appears at times to be morereactive and if in doubt as to the suitability of any particularequipment or procedure it should be cautiously explored before adoption,either on a laboratory scale, pilot plant scale, or large scale.Reactions involving glycide probably take place more rapidly and atlower temperature than allyl glycidyl ether,.for instance, at 100 to 120C. If the reaction does not take placeat this temperature, thetemperature should be increased slightly, and particularly slowly andcautiously. If the reaction does take place at this temperature andstarts to proceed too rapidly it should be controlled carefully.Briefly, the lowest temperature of reaction should beemployed which isconsistent with uniform and constant reaction without a tendency eitherto accelerate to a degree suggesting violent reaction or slowing down toa degree which indicates that any of the glycide will be left over inuncombined state.

Although ethyleneoxide and propylene oxide may represent less of ahazard than glycide, yet these reactants should be handled with extremecare. One suitable procedure involves the use of propylene oxide orbutylene oxide as a solvent as well as a reactantin the earlier stagesalong with ethylene oxide, for instance, by dissolving the appropriateresin in propylene oxide even though oxyalkylation is taking place to agreater or lesser degree. After a solution has been obtained whichrepresents the selected resin dissolved in propylene oxide or butyleneoxide, or a mixture which includes the oxyalkylated product, ethyleneoxide is added to react with the liquid mass until hydrophile propertiesare obtained. Since ethylene oxide is more reactive than propylene oxideor butylene oxide, the final product may contain some unreactedpropylene oxide or butylene oxide which can be eliminated byvolatilization or distillation in any suitable manner. See articleentitled Ethylene oxide hazards and methods of handling, Industrial andEngineering Chemisty, volume 42, No. 6, June 1950, pp. 1251- 1258.

EXAMPLE (31115- Blown allylsucrose identified as Example 35 preceding421 Ethylene oxide 990 Xylene i 421 Sodium methylate. 10

The above mixture was placed in an autoclave and adjustment made so thatthe temperature would vary between 180 to 200 C. The pressure controlwas set so that the pressure would not go above 190 p. s. i. during theoperation. The time period regulator was set so as to inject theethylene oxide in 3 hours and then continue stirring for a half hourlonger. The reaction went readily and, as a matter of fact, the ethyleneoxide could have been injected in less than an hours time and probablythe reaction would have been completed without allowing for a subsequentstirring period.

The product so obtained calculated back to composition in terms of thereactants was as follows: Per cent Blown allylsucrose 29.9 23.0 Ethyleneoxide 70.1 54.0 Xylene 23.0

The product was xylene-soluble and wateremulsifiable. EXMQLE 2U Gms.

Blown allylsucrose (same as Example 1c above) Xylene 419 Sodiummethylate 1 10 Propylene oxide 1205 Per cent Blown allylsucrose- 25.620.5 Propylene oxide 74.4 59.0 Xylene 20.5

.The product wasxylene-soluble and waterinsoluble.

EXAMPLESc 1,231 grams of the product identified as 10' preceding andrepresenting 283 grams of blown,

allylsucrose, 283 grams of xylene and 665 grams of ethylene oxide wastreated inthe same manner as before with an additional 370 grams ofethylene oxide. During this operation, the automatic equipment was setfor a maximum temperature of 200 C., a maximum pressure of 200 p. s. i.and for a reaction time of 30 minutes with a subsequent stirring periodof another 30 minutes. No additional sodium methylate was employed. Atthe end of the reaction the composition on both the xylene-free andxylene-containing basis was as follows:

Per cent Blown allylsucrose 21.5 17.7 Ethylene oxide 78.5 64.6 Xylene17.7.

The product was xylene-soluble and waterhour with a subsequent stirringperiod of one-' half hour.

The reaction. could-have been completed in considerably less time due tothe added catalyst. The composition of the product on both a xylene-freeand a xylene-containing basis is as follows:

Per cent Blown allylsucrose 10.1 9.2 Ethylene oxide 37.1 33.7 Propyleneoxide 52.8 47.9 Xylene 9.2 The product was both water soluble and xylenesoluble.

EXAMPLE 50 957 gram of the product identified as 20 preceding andrepresenting 196 grams of blown allylsucrose, 565 grams of propyleneoxide, and 196 grams of xylene was mixed with an additional 10 grams ofsodium methylate and then reacted.

with an additional 1355 grams of propylene oxide. The automatic processequipment was set to introduce the propylene oxide in an hour andstirring for an additional forty-five minutes. The equipment was set fora maximum temperature of 175 C. and a maximum pressure of 150 p. s. i.In this instance, however, the pressure never got above p. s. i. Thecomposition of the product both on a xylene-free and a xylenecontainingbasis is as follows:

Per cent Blown allylsucrose 9.2 8.5 Propylene oxide 90.8 83.0 Xylene 8.5

155 p. s. i.

' for a maximum temperature of 165 C. and for a maximum pressure of 200p. s. 1. However, in this particular instance the automatic equipmentdid notfunction properly and actually a maximum pressure of 230 p. s. i.was reached. The compositionof. the product-on both a xylene-freeandxyleneecontaining basis was as follows:

Per cent Blown allylsucrose 12.7 11.3 Propylene oxide 1 36.6 32.4Ethylene oxide 50.7 45.0 Xylene-11-62-"; 11.3

v The product was soluble in both xylene and in water.

EXAMPLE 7::

1,197 grams of the product identified as'4c andrepresenting110grams ofallylsucrose, 403, grams of ethylene, oxide, 574grams of propylene oxideand 110 grams of xylene was mixed with 5 grams of sodium methylate andthen reacted with 1,335 grams of propylene oxide. The equipment was setfor a reaction period of one hour followed by thirty minutes ofstirring. The automatic deviceswere set fora maximum temperature of 175C. and a maximum pressure of The maximum pressure reached, however,,wasonly. 110 p. s. i. The composition of theproduct on both a xylene-freeand xylenecontaining loasisv is as follows:

, Percent Blown allylsucrose i 4.5 4.25 Ethylene oxide 16.6 16.0Propylene oxide -1 78.9 75.5 Xylene 4.25

Per cent Blown allylsucros'e 5.5. 5.2 Propylene oxide 53.4 50.6Ethyleneoxide 41.1 39.0 Xylene 5.2

The product was soluble inboth' water and xylene.

EXAMPLE 90 1,045 grams of the product identified as. 7c precedingrepresenting 44 grams of blown allylsucrose, 167 grams of ethylene oxideand 790 grams of propylene oxide was treated with an additional 760grams of propylene oxide. The reaction equipment was satisfactory for amaximum temperature of 175 C. and a maximum The time was set for aforty- The product was clispersible in water and sol.- uble in xylene.

EXAMPLE 100 985 grams of the mixture identified as 50 preceding.representing 83.5 grams of blown allylsucrose, 818 grams of propyleneoxide and 63.5 grams of xylene was reacted with an additional 1,075grams or propylene oxide. The reaction time was set for an hour andone-half and the stirring period for" an additional half hour. Theequipment was set for a maximum temperature. of 185 C. and a maximumpressure of 200p. S. i.

sibly as little as a half hour. of the product on both a xylene-free andxylene-containing basis is as follows:

7 Percent Blown allylsucrose 4.2 4.0 Propylene oxide 95.8 92.0 Xylene4.0

The product is just barely dispersible in water, perhaps bettercharacterized as being insoluble but was solublein xylene.

EXAMPLE 713 grams of the product identified as 100 precedingrepresenting 28.5 grams of blown allylsucrose, 656 gramsof propyleneoxide and 28.5 grams of xylene was mixed with 5 grams of sodiummethylate and reacted with 475 grams ofethylene oxide. The equipment wasset for a reaction period offorty-five minutes and a stirring period ofan additional forty-five minutes. It: was set for a maximum temperatureof 160 C. and a maximum pressure of 180 p. s. i.

The maximumpressure reached, however, was

only 150 p. s. i. and the reaction was so fast the procedure could havebeen completed in onehalf or one-third of the time indicated. Thecomposition of the material both on a xylenefree and axylene-=containing basis is as follows:

, Per cent Blown allyls'ucrose 2.5 2.4 Propylene oxide 56.6 55.2Ethylene oxide 40.9 40.0 Xylene 2.4

The product was'soluble in both xylene and in water.

EXAMPLE 758 grams of the product identified as 100 precedingrepresenting 30.5 grams of blown allylsucrose. 697 grams of propyleneoxide and 30.5 grams of xylene was mixed with 5 grams of sodiummethylate and treated with 555 grams of propylene oxide. The equipmentwas set for a reaction period of eight hours followed by two hoursstirringon the followingday. The tem-,

perature was set for a maximum of 180C. but

pressure of 200 p. s. i. The time periodwas one hour for reaction andone hour for stirring. The maximum pressure, however; only reached p. s.i. The composition of the product both on the xylene-free andxylene-containing basis is as follows:

H V Per cent Blown allylsucrose 2.5 2.4 Ethylene oxide 9.5 9.2 Propyleneoxide 88.0 86.0 Xylene 2.4

in this instance did not reachmore than C. The pressure device was setfor a. maximum of 200 p. s. i. but failed to actproperly and thepressure actually reached 250 p; s. i. The composition of the product onboth a xylene-free and xylene-containing basis is as follows:

I Per cent Blown allylsucrose 2.4 2.3 Propylene oxide 97 .6 95.4

Xylene 2.3

Actually the pressure never reachedhigher than 150' p. s..i. and the:reaction could. havebeen completed in less. than an hour, pos-" Thecomposition 21 The product was soluble in xylene but hardly dispersiblein water. It would better be identified as water-insoluble.

The same procedure employed in Examples 10 to 120, inclusive, was usedto prepare samples from a more highly polymerized allylsucrose,particularly the kind identified as Example 2b, preceding. The procedureemployed in oxyalkylation, whether using ethylene oxide or propyleneoxide or a combination of the two, was substantially the same. In eachinstance where the compounds had present both ethylene oxide andpropylene oxide as exemplified by Examples 200 through 260 inthesucceeding table they were prepared in a variety of ways, such as,(a) first adding all the ethylene oxide and then the propylene oxide,or (b) adding the propylene oxide and then the ethylene oxide, or (0)adding a mixture of the two oxides in a single step. In

' each instance xylene was present as a solvent but other suitablesolvents such as decalin, xylene or the like, could be used. Sodiummethylate was used as a catalyst in each instance but any other catalystwould be just as satisfactory. The amount of catalyst added in theinitial stage was equivalent, roughly, to 2% of the blown allylsucrose.In the final steps if the percentage dropped much below to sufficientsodium methylate was added to bring the amount of catalyst at the end ofthe reaction up to about Caustic soda or caustic potash could be usedinstead of sodium methylate, or other catalysts could be employed, as iswell known. The solubility of the products varied, as noted, from xylenesolubility, or for that matter solubility in non-aromatic kerosene, to astage where the product was completely soluble in water and foamed inwater on shaking.

In all these instances the operating conditions were substantially thesame as far as temperature and pressure goes, i. e., oxyalkylationtemperature of 150 to 200 C. and slightly in excess thereof. and amaximum operating pressure of 150 pounds per square inch up to 220 or225 pounds per square inch. In some instances the reactions took placewith even less pressure, i. e., less than 150 pounds per square inch andrarely got slightly higher.

' Operation was about the same in all instances, 1. e., the equipmentwas set usually so as to inject anywhere from 100 to 200 grams of anoxide, up to a kilogram, per hour. The rate of stirring was about thesame, whatever was indicated as convenient, usually running from 150 R.P. M. up to 450 R. P. M. Reactions, of course, could be speeded up inevery instance by increasing the amount of catalyst; increased speed ofreaction meant that reaction would take place in less time, orat a lowertemperature, or at less pressure, or comparable conditions. As a matterof fact, using a longer period of time and an increased amount ofcatalyst oxyalkylations could be conducted at a temperatureapproximately that of the boiling point of water, for instance 95 to 115C., with practically no pressure at all, or in any event at less than 30or 40 pounds per square inch. Such procedure is well known but will bedescribed briefly subsequently.

, The appearance of all these derivatives was more or less the same.They varied from very light straw-colored viscous liquids to darkambercolored viscous liquids. This appearance was on Q. solvent ireebasis.

Table I Composition on Solvent-iree Allyl Basis, Percentage by WeightOxyalkylated Com- &2?

pound, Ex. No. Ethyll- Propylpmmd' Amt e Ex N o me one (grams) OxideOxide (grams) (grams) ouoooosmcoaowwwcaccrocco pp=gopgoppippe r-puga z zcocccooocaoocca In using other alkylene oxides, particularly glycide,the procedure was much the same except that the treatment with glycidegenerally involved the use of a glass reaction vessel as previouslydescribed. By and large the effect of glycide was about the same asadding a somewhat smaller amount of ethylene oxide. Stated another way,if a product were treated with propylene oxide and then with a smallamount of ethylene oxide substantially the same results could beobtained by adding a somewhat..de-. creased amount of glycide instead ofethylene oxide. This was true when the glycide was used also. However,different results were obtained apparently when glycide was added at anearlier stage for the reason that branching was involved. This can beillustrated by the following: If three moles of penta-allylsucrose arepolymerized to form a trimer, this trimer presumably has approximately 9hydroxyls or a few less. If this product were treated with l to 9 molesof glycide there are then available an increased number of hydroxylradicals and may be as many as twice the original number. Such product,if subjected to oxypropylation or oxyethylation or both, yields amolecule which shows a greater branching or a greater branchedstructure.

The same would apply if the trimer were first treated with ethyleneoxide and then with glycide and propylene oxide, or with propylene oxideand with glycide and then with ethylene oxide. However, since the mostsuitable compounds were obtained without the .use of glycide and usingthe cheaper alkylene oxides, to wit, ethylene oxide and propylene oxide,this phase does not require further elaboration.

In order to show the variety of materials obtainable by either the useof propylene oxide or ethylene oxide, or a combination of the two,reference is made to the hereto attached drawings, i. e., Figures 2 and3. In Figure 2 there is a trapezoidal area indicated by the numerals I,2, 3 and 4, which shows the composition of'materials derived solely fromblown allylsucrose as previously described, 1. e., the material which ismostly pentaallylsucrose. These particular compositions were effectivedemulsifiers on a number of oils tested in the Gulf Coast area.

, Reference is made to Figure 3.which,shows a number of compositionsderived not only from blown allylsucrose but also from mixtures of thekind previously described. These mixtures were particularly efiective asdemulsifiers on a number of California oils. 7

Reference is madeto Figure 4 of the hereto appended drawings in whichthe tetrahedron defined by points A, B, C, D, show the composition ofmaterials obtained from polymerized pentaaliylsucrose and propyleneoxide alone, or propyl- III in Roman numerals. These correspond to thethree points in order of increasing propylene xide content. All theremaining points numbered I to l3, inclusive, correspond to the pointsWithin the area following in a general clockwise direction, beginningnear the top. An efiort to number all these points would only cause aconfused presentation andwould detract from clarity. All these data areincorporated in the following table:

- 7 Table 2 Percentages by Weight Per cent Polymerized PentaallylsucroseBer cen Ethy1- ene Oxide PPer cent ropy ene Oxide In regard to thecompounds obtained from polymerized pentaallylsucrose and propyleneoxide alone'there is, of course, no variation possible in the. sensethat this is true in regard to' the use of combined oxides. Where bothethylene oxide and propylene oxide are used three or more variations arepossible; one can react with propylene oxide first and then withethylene oxide; or. react with ethylene oxide first and then withpropylene oxide; or simply mix the two oxides. and use a singleoxyalkylation procedure so as to get randomv oxyalkylation. Mypreference is to oxypropylate first and then use ethylene oxide.

EXAMPLE 870 Grams Polymerized pentaallylsucrose, identified as Example16-, preceding Xylene 500 Sodium methylate 10 The above mixture wasplaced in an autoclave and an adjustment made so the temperature wouldvary between C. and C. The

274 pressure control was set so the pressure. would not go above poundsper square inch during the operation. The time period regulator wassetso as to inject the propyleneoxide in three hours and then continuestirring for ahalf-hour longer. matter of fact, the propylene oxidecouldhave. been injected in less than an hours time and the reactionwould have been completedwithout allowing for a subsequent stirringperiod;

The above operation was typical. insofar that this entire series ofoxypropylations. were: conducted asa. rule within the temperature? rangeof 145 to 190C. The pressure variedfromlSO po'und'sto' 1801 poundspersquare inch. The en.-

tire time period varied from approximately; 2:

hours to 3 hours. The. catalystv used was: so-

dium methylate although caustic soda; or caustic: potash would be justas satisfactory. The-solvent used was. xylene, although any othersuitable:

solvent such as. cymene or decalin could. havebeen used. The use of thesolvent is largely a matter'of convenience. Forinstancain anauto clavewhose volume: capacity. is approximately 3 litersit is usually necessaryto have; aminimum of 300 to 500 grams in the autoclave so as to havesatisfactory regulations by mechanical devices during. the early. stagesof reaction; The. solvent; of coursaca'n be removed subsequently,

if desired, by: distillation, particularly vacuum distillation. Theautoclave was operated at a speed of about 350 R. P. M. Actually, asomewhat lower temperature could have been used buttemperaturessuch asdescribedin subsequent Table 4' eliminate any possibility of unreactedalkylene oxide being left. over at the end. of. the reaction. The timeperiod arrangement was just purely a matter of convenience generallyspeaking, anda half-hour stirring period was allowed after. the.reaction was complete simply as asafeguard and, in addition, a regulatorwas setto (iii inject the oxide in half the allotted time for thereasonthat if the automatic regulator stopped the reactionfor fifty per.cent of the. time there would still be ampletime to insure complete.introduction of oxide.

In subsequent Tables 3 and 4. there are. data in regard to thepreparation of oxyalkylat'ed derivatives in the same manner as describedin Example 370 preceding. In these examples, the propylene oxide'wasadded first as indicated.

In numerous cases the amount of ethylene oxide added was comparativelysmall as'i'n Examples 420 through 480 and 540 through 560; Intheseexamples the reaction mass was allowed to cool, the autoclaveopened and the ethylene oxide added, the autoclave swept-free withnitrogen, and then sealed, and oxyethylation permitted to take placeunder substantially the same conditions as. before. In some. instancespart of the solvent was added at the initial propylene oxide stage andsome at the ethylene. oxide stage. In some instances all the catalystwas added at the propylene oxide. stage and inother instances part atthepropylene oxide. stage and part at. the ethylene. oxide stage. Allthisis shown clearly in Table 4.. In such instances where the. amount ofethylene oxide added was sizeable, for instance, in Examples 490 through530, the automatic injectordevice' was employed although this wasunnecessary; All the oxide could have been added in a single portion;all at one time.

A second series of oxyethylations were" con-'- ducted in the samemannenin- Example- 422:

The reaction Went readily and, as athrough 560, with this difference;the ethylene oxide was added first and then the propylene oxide wasadded. Here, again, in the counterpart of Examples 420 through 480 and540 through. 560 the oxyethylations were conducted by simply injectingthe oxide in a single batch and permitting treaction to take place. Inthese instances all the solvent and all the catalyst was added at theinitial reaction stage. The reactions in all instances took place ratherrapidly, comparable to the conditions indicated in regard to ethyleneoxide in Table 4, i. e., temperature ranges of 140 C. to 160 C., and thepressure ranges were sometimes as low as 80, 90 or 100 pounds per squareinch, up to 160 pounds. The time allowed for reaction was from one hourto two hours with one-half hour for stirring. Actually, in mostinstances the reaction was complete within a few minutes and even wherethe oxide was injected in fifteen minutes, as in the counterparts .ofExamples 490 or 500, the reaction was complete in less than 45 minutes.

A third series of oxyalkylations were conducted in the same manner aspreceding, except that the ethylene oxide and propylene oxide were mixedtogether and random oxyalkylation permitted to take place. The amount ofreactants used was as used in Tables 2 and 3: the amount of catalystused represents the total amount in each instance: and the amount ofsolvent used repre- 26 oxyalkylation temperature was that indicated forpropylene oxide only in Table 4 for the reason that this was more thansuflicient and the use of ethylene oxide actually did not markedlyincrease the actual reaction time. In most instances reaction time is amatter of convenience, i. e., after the apparatus was started it waspermitted to run roughly the bulk of half a working day because thisfitted into convenience of oper:

ation.

A variety of additional derivatives were prepared simply substitutingpolymerized pentaallylsucrose identified as Example 2b or 3b preceding,in the same three series as those employing polymerizedpentaallylsucrose in Example 16 -As pointed out previously mypreferenceis, everythingelse being equal, to add, the propylene ox+ ide firstand;then the ethylene oxide where both oxides are employed.

In the various calculations in the table the amount of catalyst is shownbut is not taken into consideration in calculatingcomposition, for thereason that the catalyst can be eliminated readily by adding a suitableacid, such as HCl, refluxing the mixture with a conventionalphaseseparating trap so the xylene eliminates the water, cooling andapplying filtration so as to eliminate the sodium chloride or other saltformed. For many uses, such as demulsiflcation, the residual catalystmay remain in the sents the total amount in each instance. The mixture.

Table 3 Percent by weight Percent Solvent- PPAS or Solvent-lreeContaining- Ex. Other Grs lane PrO, EtO, No. Startin Grs. Grs. a r

Material PPAS PrO 'EtO -PPAS PrO -Et0 $3;

150 500 15 85 10 '56. 7 3313 370 1,000 500 13 87 r 9.1 60.7 30. 2 3701,000 500 s 92 as 72.4 213 38c 938 250 5 95 4. 3 '81. 2 l4. 5 38 750 1253 97 3. 7 83. 7 12. 6 1b 250 4. 5- 94 5 3.6 75.2 1.2 20

1b 250 6. 5 92 1.5 5. 2' 73. 6 I. 2 20 1b 250 7. 5 91 1.5 6. 0 72. 8 1.220 1b 45 250 4. 5 88. 5 7.0 3.6 70.- 8 5.. 6 I 20 lb 250 8. 5 86. 5 5.06. 8 69. 2 4. 0 20 j 1!) 140 250 14.0 85. 5 1. 5 11. 2 6 6 l. 2 20 1b250 13. 0 82. 5 4. 5 10. 4 66.0 3. 6 20 lb 150 250 15.0 70.0 15.0 12. 056.0 12. 0 20 lb 30 250 3.0 70.0 27. 0 2. 4 56.0 21. 6 20 lb 80 250 8.079.0 13.0 6. 4 63. 2 10. 4 21) 1b 125 250 12. 5 7 5 16.0 10.0 57. 2 l2.8 20. lb 60 250 6. 0 72.0 22. 0 4. 8 57. 6 l7. 6 20 lb 250 14. 0 79.07.0 11.2 63.2 5. 6 20' 1b 120 230 12.0 86.0 2.0 9. 6 68. 8 1.6 20 lb 85250 8.5- 89.0 2. 5 6.8 71. 2 2.0 20

1 All items are on solvent-free basis as noted in "T-t"S in next column.

Table 4 1 s 1 M Max 1 s 1 M giax' Ex Added ys 0 Pres. Time ys O Time YNa vent, temp., Na vent, temp., Lbs. Flrst Meth- Gis. 0. Hm Meth- Grs.0. sq. in.

ylate ylate Gm. Gra.

.sidered, i. .e., a much greater especially to large-scale operations.conventional equipment of the kind previously Returning now to FigureS,the points on this drawingsome. being on the'two lines whichrepresentbinary mixtures and some being in the conventional triangular area whichshows tertiary mixtures, illustrate the products which have been made,not only from such products as represented by'Examples 2b, and 3b,preceding, but also from'p-roducts obtained by the polymerizationofmixtures, such as mixtures of the kind exemplified by Examples 2a, 4a,and 5a. Such mixtures'as previously pointed out, can be subjected topolymerization to yield polymerized materials comparable .to Examples115, 2b and 3b. Such polymers derived from mixtures of allyl compoundsare just as satisfactory as far as the 'oxyalkylation step goes as thepolymers derived solely from allylsucrose. The various points on thedrawing refer to and illustrate such particular derivatives as well asthose derived from polymerized allylsucrose only.

:As has been pointed out previously oxyalkylations and particularlyoxyethylations and oxypropylations are conducted in a wide variety ofconditions, not only in regard to presence or absence of catalyst, kind.of catalyst previously described, but also in regard to the time ofreaction, temperature of reaction, speed of reaction, pressure duringreaction, etc. For instance, oxyalkylations can be conducted attemperatures up toapproximately 200 C. with pressuresin about the samerange up to about 200 pounds per square inch. They can be conducted alsoat temperatures approximating the boiling point of waterorslightlyabove, as'for example 115 to 120 C. Under such circumstances thepressure I will be less than pounds per'square inch unless somespecialprocedure is employedas is sometimes the case, to wit, keeping anatmosphere of inert gassuchas nitrogen in the vessel during thereaction. Such temperature-low reaction rate oxypropylations have beendescribed very completely in U. S. Patent No. 2,448,664 to H. R. Fife-cta1., dated September 7, 1948. Low temperature, low pressureoxypropylations are particularly desirable where the compound beingsubjected to oxypropylation'contains one, two or three points ofreaction only, such as monohydric alcohols, glycols and triols.

The same procedure can be employed in polyhy'droxylated materials of thekind herein de- U scribed. Probably less byproducts are formed but-theeconomy of theprocedure must be con length of reaction time. 7

Since low pressure, low temperature reaction "speed oxypropylationsrequire considerable time,

for instance, 1 to 7 days of 24 hourseach to complete the reaction, theyare conducted as a rule whether-on a laboratory scale, pilot plantscale, or large scale, so as to operate automat-- ically. The priorfigure of seven days applies I have used described with two addedautomatic features: (a) a solenoid controlled valve which shuts oil thepropylene oxide in event that the temperature gets outside apredetermined and set range, for instance, 110 to 120 C., and (21)another solenoid valve which shuts oil the propylene oxide (or for thatmatter ethylene'oxide if it is being used) if the pressure gets beyond apredeterminedrange, such as 25 to pounds. Otherwise, the equipmentissubstantially the same as is commonly employed for this purpose where3 the pressure of reaction is much shorter. In

such instances such automatic controls are not necessarily used.

Thus, althoughthe various examples previously noted have been preparedat comparatively high temperatures and pressures. Ihave prepared a fewat low pressures using laboratory equip ment which is designed to permitcontinuous oxyalkylation whether it be oxyprcpylation or oxyethylation.

In a general way'I have started out "with approximately three to fivetimes as much cata .lyst as when higher temperatures wereemployed.

In many cases the time or addition was tento twenty times-as longIasllO"C.,;as.'at 160 to C. 'The final; productalso'hadmoreresidual catalyst,.in mostinstances from 93% to l /l2% as compared with /2'% or less inthe'higher temperature procedure. If .the presence of an increasedamount of catalyst at the end of the reaction is objectionable,naturally this is another objection to using the low temperature andlong reaction time procedure. 7 It is sometimes a nuisance and addedexpense to remove such excessive amount of alkaline catalyst. 7

Attention is directed to the fact that a number of the'hereto attachedclaims are characterized by the fact that there is the added provisothat the hydrophile properties of said oxyalkylated derivative in anequal weight of xylene are sufiicient to produce an emulsion when saidxylene solution is shaken'vigorously With'one to three volumes of Water.

.As has been pointed out previously, there is a wide variety of suitablepolymers which can be subjected to oxyalkylation by one or more of thealkylene oxides specified or by a mixture of the same. For instance, onemight partially oxyalkylate with ethylene oxide and then finish oil"with propylene oxide. Previous examples il1us- 'trate such procedure.

Having obtained'a suitable allylsucrose or ally sucrose mixture polymerof the kind described. such allylsucrose polymer is subjected totreatment With a low molal reactive alpha-beta ole- 'fin oxide so as torender the product distinctly hydrophile in nature as indicated by thefact that it becomes self-emulsifiable or miscible or In ethylene oxide,the oxygen-carbon ratio is 1:2. In glycide, it is 2:3; and in methylglycide 1:22. In such compounds the ratio-is very favorable to theproduction of hydrophile or surfaceactive properties. However, theratio, in propylene oxide, is 1:3, and in butylene oxidelzi. Obviously,such latter two reactants are satisfactorily employed only when theallylsucrose composition is such as to make incorporation of the desiredproperty practical. In other cases, they may produce marginallysatisfactory derivativesj, or even unsatisfactory derivatives. They areusable in conjunction with the'three more favorable alkylene oxides inall cases. For

to maximum hydrophile properties.

'29 instance, after one orseveral propylene oxide or butylene oxidemolecules have been attached to the allylsucrose polymer, oxyalkylationmay be satisfactorily continued using the more favorable members of theclass, to produce the desired hydrophile product. Used alone, these tworeagents may in some cases fail to produce sufllciently hydrophilederivatives because of their relatively low oxygen-carbon ratios.

Thus, ethylene oxide is much more effective than propylene oxide, andpropylene oxide is more effective than butylene oxide. Hydroxypropyleneoxide (glycide) is more effective than propylene oxide. Similarly,hydroxy butylene oxide (methyl glycide) is more effective than butyleneoxide. Since ethylene oxide is the cheapest alkylene oxide available andis reactive, its use is definitely advantageous, and especially in lightof its high oxygen content. Propylene oxide is less reactive thanethylene oxide, and butylene oxide is definitely less reactive thanpropylene oxide.

Considerable of what is said immediately hereinafter is concerned withthe ability to'vary the hydrophile properties of the compounds used inif the process from minimum hydrophile properties Even more remarkable,and equally diflicult to explain, are the versatility and utility ofthese compounds as one goes from minimum hydrophile property 'toultimate maximum hydrophile property.

In a general way approximate minimum hydrophile property may bedetermined by solubility. Such minimum hydrophile property orsub-surface activity or minimum surface-activity means that the productshows at least emulsifying properties or self-dispersion in cold or evenin warm distilled water (15 to 40 C.) in concentrations of 0.5% to 5.0%.These materials are generally more soluble in cold water than warmwater, and may even be very insoluble in boiling water. Moderately hightemperatures aid in reducing the viscosity of the solute underexamination. Sometimes if one continues to shake a hot solution,

even though cloudy or containing an insoluble r phase, one finds thatsolution takes place to give a homogeneous phase as the mixture cools.Such self-dispersion tests are conducted in the absence of an insolublesolvent.

In a number of instances one can determine the fact that one is past'theminimum hydrophilehydrophobe balance, or at least in an optimum zoneeven though one does not obtain a sol as described immediatelypreceding, by the fact that the hydrophile character is indicated by theproduction of an emulsion. For instance, one can prepare an emulsionthat contains an inert solvent such as xylene to the extent of 10% to 50All that one needs to do is to have a xylene solution within the rangeof 50 to 90 parts by weight of oxyalkylated derivatives and 50 to 10parts by weight of xylene and mix such solution with one, two or threetimes its volume of distilled water and shake vigorously so as to obtainan emulsion which may beof the oil-in-water type ylene glycoldiethylether, or diethylene glycol diethylether, with a little acetoneadded if required, making a rather concentrated solution,

for instance 40 to 50%, and then adding enough of the concentratedalcoholic or equivalent solution to give the previously suggested 0.5%to 5.0%

'; dispersion is referred to as at least semi-stable in the sense thatsols, emulsions, or dispersions prepared are relatively stable, if theyremain at least for some period of time, for instance 30 minutes to 2hours, before showing any marked separation. Such tests are conductedat'room tem-- perature (22 0.). Needless to say, a test can be made inpresence of an insoluble solvent such as 5% to 15% of xylene, as notedin previous examples. If such mixture, 1. e., containing awater-insoluble solvent, is at least semi-stable, obviously thesolvent-free product would be even more so. Surface-activityrepresenting an advanced hydrophile-hydrophobe balance can also bedetermined by the use of conventional measurements hereinafterdescribed. One outstanding characteristic property indicatingsurfaceactivity in a material is the ability to form a permanent foam indilute aqueous solution, for example, less than 0.5%, when in the higheroxyalkylated stage, and to form an emulsion in the lower andintermediate stages of oxyalkylation.

Allowance must be made for the presence of a solvent in the finalproduct in relation to the hydrophile properties of the final product.The principle involved in the manufacture of the herein specifiedcompounds for use as demulsifying agents, or for other uses, is based onthe conversion of a hydrophobe or non-hydrophile compound or mixture ofcompounds into products which are distinctly hydrophile at least to theextent that they have emulsifying properties or are self-emulsifying;that is, when shaken with water they produce stable or semi-stablesuspensions, or, in the presence of a water-insoluble solvent, such asxylene, an emulsion. In demulsification, it is sometimes preferable touse a product having markedly enhanced hydrophile properties over andabove the initial stage of selfemulsifiability, although I have foundthat with products of the type used herein, most efficacious results areobtained with products which do not have hydrophile properties beyondthe stage of self-dispersibility.

More highly oxyalkylated allylsucrose polymers give colloidal solutionsor sols which show typical properties comparable to ordinarysurface-active agents. Such conventional surfaceactivity may be measuredby determining the surface tension and the interfacial tension againstparafiin oil or the like. At the initial and lower stages ofoxyalkylation, surface-activity is not suitably determined in this samemanner but one may employ an emulsification test. Emulsions come intoexistence as a rule through the presence of a surface-active emulsifyingagent. Some-surface-active emulsifying agents such as mahogany soap mayproduce a water-in-oil emulsion or an oil-in-water emulsion dependingupon the ratio of the two phases, degree of agitation, concentration ofemulsifying agent, etc.

The same is true in regard to the oxyalkylated allylsucrose polymersherein specified, particularly in the lower stage of oxyalkylation, thesocalled sub-surface-active stage. The surfaceactive properties arereadily demonstrated by Proof water and shaken to produce an emulsion.

The amount of xylene is invariably sufdcient to reduce even a tackyresinous product to a solution which isreadilyid-ispersible. Theemulsions so'produced are usually xylene-in-water emulsions(oilsin-wa'ter type) particularly when the amountof distilled water usedis at least slightly in excess of the volume of xylene solution and alsoif shaken vigorously. At times, particularly in the lowest stage ofoxyaikylation, one may obtain a water-inexyleneemulsion (Water-sin-oiltype.) which is apt to reverse on more vigorous shaking and furtherdilution with water.

.In a few instances the allylsucrose polymer may not be sufficientlysoluble in xylene alone but may require the addition of some ethyleneglycol diethyl ether as described elsewhere. It

'is understood that such mixture, or any other similar mixture, isconsidered the equivalent of xylene for the purpose of this test.

In many cases there is no doubt as to the presence or absence ofhydrophile or surface-active characteristics in the products used inaccordance with this invention. They dissolve or disperse in water;andsuch dispersions foam readily. With borderline cases, i. e., thosewhich show only incipient hydrophile or surface-active property(-sub-surface-activity) tests for emulsifying properties orself-disp'ersibility are useful. The fact that a reagent is capable ofproducing a dispersion in water is proof that it is distinctlyhydrophile.

The presence'cf xylene or an equivalent waterinsclublesolvent maymaskthe. point at which a solvent-free product on mere dilution in a testtube exhibits self emulsification. For this reason, .if it is desirableto determine the'approximate point where seli-emulsification begins,then it is better to eliminate the xylene or equivalent from a-smallportion of the reaction mixture'and test such portion. In some cases,such xylenefree resultant may show'initial or incipient hydrophileproperties, whereas in presence of xylene such properties'would not benoted. In other cases the first objective indication of hydrophileproperties may be the capacity of the material to emulsify an insolublesolvent such as xylene.

It is to be emphasized that hydrophile properties products useful forthe practice or "this invention. .Another variation is the molecularsizeof the allylsucrose polymer as herein described.

I Numerous hydroxylated allyl compounds have been described other thanallylsucrose. Such compounds, other than allylsucrose, are suitable forthe formation of a polymeric mixture as described. Obviously thepolymerization of such other compounds alone (other than allylsucrose)which yield oxyalkylation-susceptible polymers can be used to giveorganic solvent-soluble polymers which in turn can be reacted with thesame alkylene oxides in the same. manner so as to give herein referredto are such as those exhibited by incipient self-emulsification or thepresence of emulsifying properties and go through the range ofhomogeneous dispersibility or admixture with water even in presence ofadded water-insoluble solvent and minorpropor-tions of commonelectrolytes as occur in oil field brines.

Elsewhere, it is pointed out that an emulsifi- -catien test may be usedto determine ranges of surface-activity and that such emulsificationtests employ a xylene solution. Stated. another way, it is reallyimmaterial whether a xylene solution produces a sol :or whether itmerely pro duces an emulsion. Y

In light of what has been said previously in reg'ardto the variation ofrange of hydrophile properties, and also in light-of what has been saidas to the variation in the effectiveness of various alkylene oxides, andmost particularly of all ethylene oxide, to introduce hydrophileemployed or other alkylene oxide, for producing analogues of thecompounds herein described in detail. Not only thatybut such compoundscan be mixed with each other or with non-hydroxylated allyl compoundsand such mixtures treated inthe same manner. The various oxyalkylationproducts so obtained and particularly those in which the amount of thepolymer is not over 10% and in which the amount of propylene oxide is ormore, and the amount of ethylene oxide is comparatively small, forinstance, less than 20% and usually less than 10%, serve as effectivedemulsifiers in the same manner as described elsewhere herein. Thepreceding percentages are by weight. They are useful also for otherpurposes, such as additives in making emulsions or as emulsifiers. It isto be noted,-however, that this particular class, or classes, ofmaterials and their uses as demulsifiers and for other purposes is notclaimed in the instant application. 7

PART 4 Attention is directed to the fact that the herein describedcompounds, compositions and the like which are particularly adapted foruse as depound insofar that they are efiective and valuable demulsifyingagents for resolution of waterin-oil emulsions as found in the petroleumindustry, as break inducers in doctor treatment of sour crude, etc.

Such hydroxylated compounds can be treated with various reactants suchas epichlorohydrin, dimethyl sulfate, sulfuric acid, maleic anhydride,ethylene imine, etc. If treated with epichlorohydrin or monochloroaceticacid the resultant product can be further reacted with a tertiary aminesuch as pyridine, or the like, to give quaternary ammonium compounds. Iftreated with maleic anhydride to give a total ester the resultant canbetreated with sodium bisulfite to yield a sulfosuccinate. Sulfo groupscan be introduced also by means of a sulfating agent as previouslysuggested, or by treating the chloroacetic acid resultant withsodiumsulfite.

However, the class of derivatives most readily prepared in wide varietyare the esters of monocarboxy and polycarboxy acids. 7

Assuming a typical derivative which can be indicated thus:

Rowmmmcauonn the ester of the monocarboxy acid is as follows: i o

aowamouwimowta The acid ester of a dicarboxy acid is as follows:

R0(C:HO),.(C H O)n' R-R-OOOH The complete ester of a dicarboxy acid isas follows The chloracetic acid ester is as follows:

The quaternary compound obtained by reacting the above-mentioned productwith pyridine is as follows Among the various kinds of monocarboxy acidssuitable for preparation of esters are the alpha certaindrastically-oxidized hydroxy acetylated castor oil fatty acids. Thedrastically-oxidized acetylated ricinoleic acid compounds are employedto furnish the acylradical of the ester. In this particular instance, asin all other instances, one may prepare either a total ester or apartial ester, and when carboxy acids are employed one may have not onlypartial esters which have residual hydroxyl radicals or residual carboxyradi- "cals, but also partial esters in which both are present.

A somewhat similar type of ester is obtained from hydroxy acetylateddrastically-oxidized castor oil fatty acids. It is to be pointed outthat hydroxy acetylation may take place first, and

drastic oxidation subsequently, or the reverse may be true, or bothprocedures may be conducted simultaneously. In any event, such productssupply acyl radicals of one type of ester herein included.

Another somewhat similar class are esters obtained from hydroxyacetylated drastically-oxidized dehydrated ricinoleic acid. In thisclass ricinoleic acid, castor oil, or the like, is subjected todehydration as an initial step. Such products may be employed to supplythe acyl radical of one type of ester herein included.

Another type of ester which may be employed I is a sulfo fatty acidester in which there is preseat at least 8 and not more than 22 carbonatoms in the fatty acid radical. The sulfo radical includes both theacid sulfonates and the sulfonic acids. Briefly stated, suitable sulfoacids herein employed as reactants are sulfo oleic, sulfo ricinoleic,sulfo aromatic fatty acids obtained, for example, from benzene, toluene,xylene, etc., and oleic acid or some other unsaturated acid.

Another class of acids are polycarboxy acids such as commonly used informing plasticizers, polyester resins, etc. One may use a tricarboxyacid, such as tricarballylic acid, or citric acid, but my preference isto employ a dicarboxy acid, or acid anhydride, such as oxalic acid,maleic acid, tartaric acid, citraconic acid, phthalic acid, adipic acid,succinic acid, azelaic acid, sebacic acid, adduct acids obtained byreaction between maleic anhydride and citraconic anhydride, and eitherbutadiene or cyclopentadiene. Oxalic acid is not quite as satisfactoryas some of the other acids, due to its tendency to decompose. In lightof raw material costs it is my preference to use phthalic anhydride,maleic anhydride, citraconic anhydride, diglycollic acid, adipic acidand certain other acids in the same price range which are both cheap andheat-resistant. One may also use adduct acids of the diene or clockertype.

Another class of esters are derived from certain high molal monocarboxyacids. It is well known that certain monocarboxy organic acidscontaining 8 carbon atoms or more, and not more than 32 carbon atoms,are characterized by the fact that they combine with alkalies to producesoap or soaplike materials. These detergent-forming acids include fattyacids, resin acids, petroleum acids, etc. For the sake'of convenience,these acids will be indicated by the formula R.COOH. Certain derivativesof detergent-forming acids react with alkali to produce soap or soaplikematerials and are the obvious equivalent of the unchanged or unmodifieddetergent-forming acids. For instance, instead of fatty acids one mightemploy the chlorinated fatty acids. Instead of the resin acids, onemight employ the hydrogenated resin acids. Instead of naphthenic acids,one might employ brominated naphthenic acids,

etc.

The fatty acids are of the type commonly referred to as higher fattyacids; and, of course, this is also true in regard to derivatives of thekind indicated, insofar that such derivatives are obtained from higherfatty acids. The petroleum acids include not only naturally-occurringnaphtheni-c acids, but also acids obtained by the oxidation of wax,paraffin, etc. Such acids may have as many as "32 carbon atoms. Forinstance, see U. S. Patent No. 2,242,837 dated May 20, 1941, to Shields.

The monocarboxy detergent-forming esters of the oxyalkylated derivativesherein described, are preferably derived from unsaturated fatty acidshaving 18 carbon atoms. Such unsaturated fatty acids include oleic acid,ricinoleic acid, linoleic acid, etc. for example, the fatty acidsobtained from hydrolysis of cottonseed oil, soyabean oil, etc. It is myultimate preference that the esters of the kind herein contemplated bederived from unsaturated fatty acids, and more especially, unsaturatedfatty acids containing a hydroxyl radical, or unsaturated fatty acidswhich have been subjected to oxidation. In addition to synthetic carboxyacids obtained by the oxidation of paraffins or the like, there is thesomewhat analogous class obtained by treating carbon di- One may employmixed fatty acids as, r

, 35 oxide or carbon monoxide, in the presence of hydrogen or anolefine, with steam, or by causing a halogenated hydrocarbon toreactwith potassium cyanide and saponifying the product obtained. Suchproducts or mixtures thereof, having at least 8 and not more than 32carbon atoms, and having at least one carboxyl group or the equivalentthereof, are suitable as detergentforming monocarboxy acids; and anotheranalogous class equally suitable is the mixture of car- 'box'ylic acidsobtained by the alkali treatment of alcohols of high molecular weightformed in the catalytic hydrogenation of carbon monoxide.

One may have esters derived not only from a single class of acids of thekind described, but also from more than one class, i. e., one may employmixed'esters such as esters obtained, for example, from high molaldetergent-forming acids having 8 to 22 carbon atoms, as previouslydescribed, in combination with acids of the alpha halogen carboxy typehaving less than 8 carbon atoms, such as chloroacetic acid, bromoaceticacid, etc., as previously described.

. 'Drastically-oxidized oil, such as drasticallyoxidized castor oil, ordrastically-oxidized dehydrated castor oil, may be employed to supplythe acyl radical. In other instances, one may produce mixed esters byusing polycarboxy acids, such as phthalic acid, diglycollic acid, etc.,in combination with detergent-forming acids, such as oleic acid, stearicacid, naphthenic acid, etc. Other carboxy acids may be employed in whichthere is also a sulfo group present, such as sulfo phthalic, sulfobenzoic, sulfo succinic, etc. Esters may be obtained from low molalhydroxylated acids having less than 8 carbon atoms, such ashydroxyacetic acid, lactic acid, etc. Similarly, one may employ lowmolal aliphatic'acids having less than 8 carbon atoms, such as aceticacid, butyric acid, etc. Similarly, one may employ low molal acidshaving the vinyl radical, such as acrylic acid, methacrylic acid,crotonic acid, etc. It will be noted that these acids contain variousnumbers of acyl radicals varying generally up to 22 carbon atoms for themonocarboxy acids, and

as many as 36 carbon atoms in the case of certain polycarboxy acids,particularly the dimer obtained by the dimerization of9,11-octadecandienic acid. As to this particular product, see U. S.

. Patent No. 2,347,562, dated April 25, 1944, to

Johnston.

Other suitable acids are cyclic .monocarboxy acids having not over 32carbon atoms. Examples of such acids include, cyclohexane acetic acid,

cyclohexane butyric acid, cyclohexane propionic acid, cyclohexanecaproic acid, benzoic acid,

salicylic acid, phenoxy acetic acid, etc.

The preparation of such esters are conventiona1 and do not requireelaborate description. Generally speaking, our procedure is toreact theappropriate'amount of a selected hydroxylated compound with the freeacid in presence of a high boiling solvent, such as xylene, using 1% to2% of para-toluene sulfonic acid along with a phaseseparating trap untilthe amount of water indicates the reaction is complete, or substantiallycomplete. The time required is usually 4: to 20 hours. Such esters are,as previously stated, very efiective for resolution of water-in-oilemulsions as found in the petroleum industry. 7

Thi application is a consolidation of and continuation of my priorapplications Serial Nos. 173,048, now abandoned, and 173,050; nowabandoned, filed July 11', 1950;

Having thus described my invention, what claim as new and desire tosecure by Letters Patent, is:

1. Hydrophile synthetic product; said hydrophile synthetic product beingan oxyalkylation product of (A) an alpha-beta 'alkylene oxide selectedfrom the class consisting of ethylene oxide, propylene oxide, butyleneoxide, glycide, methylglycide, methyl glycidyl ether, ethyl glycidylether and propyl glycidyl ether; and (B) an organic solvent-soluble,oxyalkylation-susceptible, hydroxylated polymerization product of amember of the class consisting of allylsucrose, and allylsucrose incombination with other co-polymerizable allyl compounds; in saidcombination the weight percentage of allylsucrose being not less than10% and not over 90%. i

2. Hydrophile synthetic product; said hydrophile synthetic product beingan oxyalkylation product of (A) an alpha-beta alkylene oxide selectedfrom the class consisting of ethylene oxide, propylene oxide, butyleneoxide, .glycide, methylglycide, methyl glycidyl ether, ethyl glycidylether and propyl glycidyl ether; and (B) an organic solvent-soluble,oxyalkylation-susceptible, hydroxylated polymerization product of amember of "the class consisting of allylsucrose, and allylsucrose incombination with other co-polymerizable allyl compounds; in saidcombination the weight percentage of allylsucrose being not less than10% organic solvent-soluble, and the allylsucrose is characterized byhaving at least a plurality of allyl radicals, and a plurality ofhydroxyl radicals. r

6. The product of claim '2 wherein the polymerized allyl derivative iswater-insoluble and organic solvent-soluble, and the allylsucrose ischaracterized by having at least a plurality of allyl radicals, and aplurality of hydroxyl radicals; and with the final proviso that thehydrophile properties'of said oxyalkylated derivative in an equal weightof xylene are sufiicient to produce an emulsion when said xylenesolution is shaken vigorously with one to three volumes of water.

7. Hydrophile synthetic product; said hydrophile synthetic product beingan oxyalkylation product of (A) an alpha-beta alkylene oxide selectedfrom the class consisting of ethylene oxide, propylene oxide, butyleneoxide, glyci'cle, methylglycide, methyl glycidyl ether, ethyl glycidylether and propyl glycidyl ether; and (B) an organic solvent-soluble,oxyalkylation-susceptible, hydroxylated polymerization product ofallylsucrose in which there is present a plurality of ally'l'radicals;and with the final proviso that the hydrophile properties of saidoxyalkylated derivative in an equal weight of xylene are sufiicient toproduce an emulsion when said Xylene solution is shaken vigorously withone to three volumes of water.

8. Hydrophile synthetic product; said hydrophile synthetic product beingan :oxyalkylation

1. HYDROPHILE SYNTHETIC PRODUCT; SAID HYDROPHILE SYNTHETIC PRODUCT BEINGAN OXYALKLYATION PRODUCT OF (A) AN ALPHA-BETA ALKYLENE OXIDE SELECTEDFROM THE CLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENEOXIDE, GLYCIDE, METHYLGLYCIDE, METHYL GLYCIDYL ETHER, ETHYL GLYCIDYLETHYL AND PROPYL GLYCIDYL ETHER; AND (B) AN ORGANIC SOLVENT-SOLUBLE,OXYALKYLATION-SUSCEPTIBLE, HY-